Magnesium-containing complexes, method for their preparation, and compositions containing the same

ABSTRACT

Magnesium-containing complexes are prepared by heating a mixture of magnesium hydroxide, magnesium oxide, hydrated magnesium oxide or a magnesium alkoxide; a carboxylic acid, a sulfonic acid, a pentavalent phosphorus acid, or an ester or salt of any of these; water; and an organic solubilizing agent (which may be liquid or solid at ambient temperature) for the acid or ester. The amount of magnesium is such as to provide a basic composition. The resulting complexes may be obtained in liquid (which may be thickened) or solid form, and are useful as additives for lubricants and fuels and as protective coating compositions for metal surfaces (such as automotive undercoats and frame coatings).

This application is a continuation-in-part of copending application Ser.No. 681,627, filed Apr. 29, 1976 and now abandoned.

INTRODUCTION AND SUMMARY OF THE INVENTION

This invention relates to new magnesium-containing compositions ofmatter and methods for their preparation. More particularly, it relatesto non-carbonated magnesium-containing complexes which are prepared byheating, at a temperature above about 30° C., a mixture comprising:

(A) At least one of magnesium hydroxide, magnesium oxide, hydratedmagnesium oxide or a magnesium alkoxide;

(B) At least one oleophilic organic reagent comprising a carboxylicacid, a sulfonic acid, a pentavalent phosphorus acid, or an ester oralkali metal or alkaline earth metal salt of any of these;

(C) Water; and

(D) At least one organic solubilizing agent for component B;

the ratio of equivalents of magnesium to component B, calculated as thefree carboxylic or sulfonic acid or as the phosphoric acid ester, beingat least about 5:1, and the amount of water present being at leastsufficient to hydrate a substantial proportion of component A calculatedas magnesium oxide.

Several methods are known for the preparation of basic magnesiumcompounds for use in lubricants, greases and the like. For example, U.S.Pat. No. 3,865,737 describes the formation of a highly basicmagnesium-containing liquid dispersion by mixing an oil-solubledispersing agent, magnesium oxide, a volatile aliphatic hydrocarbonsolvent, alcohol, watr and ammonia or an ammonium compound, treating themixture with carbon dioxide, adding a non-volatile diluent oil andremoving volatiles. Similarly, U.S. Pat. No. 3,629,109 describes thecarbonation of a mixture of an oil-soluble organic acid or salt thereof,magnesium oxide, a lower aliphatic alcohol, water and an organic liquiddiluent. The products obtained by these methods may be characterized,for the most part, as basic, oleophilic magnesium carbonates since anessential step in their preparation is reaction with carbon dioxide.

In accordance with the present invention, it has been discovered thathighly basic magnesium complexes may be prepared without reaction withcarbon dioxide or similar acidic gases. The products obtained inaccordance with the present invention, which may be characterized ascomplexes of magnesium oxide or hydroxide and a magnesium sulfonate,carboxylate or phosphate, and which are hereinafter sometimes referredto merely as "magnesium complexes", have a wide variety of uses,including additives for lubricants and fuel oils and corrosion-resistantcoatings or constituents thereof.

A principal object of the present invention, therefore, is to providenew oleophilic magnesium-containing compositions and a method for theirpreparation.

A further object is to provide a method for producing magnesiumcomplexes which does not necessitate reaction with carbon dioxide or asimilar acidic gas.

A further object is to provide basic magnesium compositions which may beobtained either in free-flowing liquid form or in thickened or solidform.

Still another object is to provide magnesium-containing compositionsuseful as greases, as detergent additives for lubricants or as corrosioninhibitors, vanadium scavengers and smoke suppressants for fuels, and inthe formulation of corrosion-resistant coatings for metals.

Other objects will in part be obvious and will in part appearhereinafter.

COMPONENT A

Component A used in the method of this invention is magnesium hydroxide,magnesium oxide, hydrated magnesium oxide, a magnesium alkoxide, or amixture of these. Magnesium hydroxide and magnesium oxide are, ofcourse, represented by the formulas Mg(OH)₂ and MgO, respectively.Magnesium oxide exists in an inactive "dead burned" and a hydratable"reactive" form and the latter is the one which is useful in thisinvention although mixtures of the "reactive" form with minor amounts ofthe "dead burned" form may also be used. "Hydrated magnesium oxide", forthe purpose of this invention, is magnesium oxide which is associatedwith water in an amount less than that required for conversion tomagnesium hydroxide; that is, the amount of water is less than one moleper mole of magnesium oxide. As so defined, "hydrated magnesium oxide"may actually be a mixture of various proportions of magnesium oxide andmagnesium hydroxide and its exact chemical nature is not critical tothis invention. Typically, the amount of water present in "hydratedmagnesium oxide" is at least about 0.7 mole per mole of the oxide.

The magnesium alkoxides, especially the lower alkoxides (i.e., those inwhich the alkyl groups contain 7 carbon atoms or less), are equivalentto magnesium oxide and hydroxide for the purpose of this invention; theyare hydrolyzed by water to magnesium hydroxide under the conditionsdescribed hereinafter.

The equivalent weight of component A is half its molecular weight, sincemagnesium is a divalent element.

COMPONENT B

Component B is at least one oleophilic reagent comprising any of severaltypes of organic acidic compounds or salts or esters thereof. Among thesuitable reagents for this purpose are the carboxylic and sulfonicacids. These acids include many of those known to be susceptible tooverbasing and especially many of those disclosed in a number of U.S.Pat. Nos. such as 2,616,904; 2,695,910; 3,312,618; 3,746,643; 3,764,533;and the aforementioned 3,629,109. Those patents are incorporated byreference herein for their disclosure of suitable acidic oleophilicreagents.

The sulfonic acids suitable for use as component B include thoserepresented by the formulas R¹ (SO₃ H)_(r) and (R²)_(x) T(SO₃ H)_(y). Inthese formulas, R¹ is an aliphatic or aliphatic-substitutedcycloaliphatic hydrocarbon or essentially hydrocarbon radical free fromacetylenic unsaturation and containing up to about 60 carbon atoms. WhenR¹ is aliphatic, it usually contains at least about 15-18 carbon atoms;when it is an aliphatic-substituted cycloaliphatic radical, thealiphatic substituents usually contain a total of at least about 12carbon atoms. Examples of R¹ are alkyl, alkenyl and alkoxy-alkylradicals, and aliphatic-substituted cycloaliphatic radicals wherein thealiphatic substituents are alkyl, alkenyl, alkoxy, alkoxyalkyl,carboxyalkyl and the like. Generally, the cycloaliphatic nucleus isderived from a cycloalkane or a cycloalkene such as cyclopentane,cyclohexane, cyclohexene or cyclopentene. Specific examples of R¹ arecetylcyclohexyl, laurylcyclohexyl, cetyloxyethyl, octadecenyl, andradicals derived from petroleum, saturated and unsaturated paraffin wax,and olefin polymers including polymerized monoolefins and diolefinscontaining about 1-8 carbon atoms per olefinic monomer unit. R¹ can alsocontain other substituents such as phenyl, cycloalkyl, hydroxy,mercapto, halo, nitro, amino, nitroso, lower alkoxy, loweralkylmercapto, carboxy, carbalkoxy, oxo or thio, or interrupting groupssuch as --NH--, --O-- or --S--, as long as the essentially hydrocarboncharacter thereof is not destroyed.

R² is generally a hydrocarbon or essentially hydrocarbon radical freefrom acetylenic unsaturation and containing about 4-60 aliphatic carbonatoms, preferably an aliphatic hydrocarbon radical such as alkyl oralkenyl. It may also, however, contain substituents or interruptinggroups such as those enumerated above provided the essentiallyhydrocarbon character thereof is retained. In general, the non-carbonatoms present in R¹ or R² do not account for more than 10% of the totalweight thereof.

The radical T is a cyclic nucleus which may be derived from an aromatichydrocarbon such a benzene, naphthalene, anthracene or biphenyl, or froma heterocyclic compound such as pyridine, indole or isoindole.Ordinarily, T is an aromatic hydrocarbon nucleus, especially a benzeneor naphthalene nucleus.

The subscript x is at least 1 and is generally 1-3. The subscripts r andy have an average value of about 1-4 per molecule and are generally also1.

Illustrative sulfonic acids useful as component B are mahogany sulfonicacids, petrolatum sulfonic acids, mono- and polywax-substitutednaphthalene sulfonic acids, cetylchlorobenzene sulfonic acids,cetylphenol sulfonic acids, cetylphenol disulfide sulfonic acids,cetoxycapryl benzene sulfonic acids, dicetyl thianthrene sulfonic acids,di-lauryl beta-naphthol sulfonic acids, dicapryl nitronaphthalenesulfonic acids, paraffin wax sulfonic acids, unsaturated paraffin waxsulfonic acids, hydroxy-substituted paraffin wax sulfonic acids,tetraisobutylene sulfonic acids, tetra-amylene sulfonic acids,chloro-substituted paraffin wax sulfonic acids, nitroso-substitutedparaffin wax sulfonic acids, petroleum naphthene sulfonic acids,cetylcyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic acids, mono-and polywax-substituted cyclohexyl sulfonic acids, postdodecylbenzenesulfonic acids, "dimer alkylate" sulfonic acids, and the like. Thesesulfonic acids are wellknown in the art and require no furtherdiscussion herein.

For the purpose of this invention, the equivalent weight of a sulfonicacid is the molecular weight thereof divided by the number of sulfonicacid groups present therein. Thus, for a monosulfonic acid theequivalent weight is equal to the molecular weight.

Carboxylic acids suitable for use as component B include aliphatic,cycloaliphatic and aromatic mono- and polybasic carboxylic acids freefrom acetylenic unsaturation, including naphthenic acids, alkyl- oralkenyl-substituted cyclopentanoic acids, alkyl- or alkenyl-substitutedcyclohexanoic acids, and alkyl- or alkenyl-substituted aromaticcarboxylic acids. The aliphatic acids generally contain at least 8 andpreferably at least 12 carbon atoms. The cycloaliphatic and aliphaticcarboxylic acids can be saturated or unsaturated. Specific examplesinclude 2-ethylhexanoic acid, linolenic acid, propylenetetramer-substituted maleic acid, behenic acid, isostearic acid,pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauricacid, oleic acid, ricinoleic acid, undecylic acid,dioctylcyclopentanecarboxylic acid, myristic acid,dilauryldecahydronaphthalenecarboxylic acid,stearyl-octahydroindenecarboxylic acid, palmitic acid, acids formed byoxidation of petrolatum or of hydrocarbon waxes, and commerciallyavailable mixtures of two or more carboxylic acids such as tall oilacids, rosin acids, and the like. The equivalent weight of any such acidis its molecular weight divided by the number of carboxy groups presenttherein.

The pentavalent phosphorus acids useful as component B may berepresented by the formula ##STR1## wherein each of R³ and R⁴ ishydrogen or a hydrocarbon or essentially hydrocarbon radical preferablyhaving about 4-25 carbon atoms, at least one of R³ and R⁴ beinghydrocarbon or essentially hydrocarbon; each of X¹, X², X³ and X⁴ isoxygen or sulfur; and each of a and b is 0 or 1. Thus, it will beappreciated that the phosphorus acid may be an organophosphoric,phosphonic or phosphinic acid, or a thio analog of any of these. Theequivalent weight of such a phosphorus acid is its molecular weightdivided by the number of hydroxy groups bonded to phosphorus therein.

Usually, the phosphorus acids are those of the formula ##STR2## whereinR³ is a phenyl radical or (preferably) an alkyl radical having up to 18carbon atoms, and R⁴ is hydrogen or a similar phenyl or alkyl radical.Mixtures of such phosphorus acids are often preferred because of theirease of preparation.

Also useful as component B are the alkali metal and alkaline earth metalsalts (e.g., sodium, potassium, magnesium, calcium, strontium or bariumsalts, with magnesium salts being preferred) and esters of the acidspreviously described. The suitable esters include those with monohydricalcohols free from acetylenic unsaturation and having about 1-25 carbonatoms, including monohydric alcohols such as methanol, ethanol, thebutanols, the hexanols, allyl alcohol, crotyl alcohol, stearyl alcoholand oleyl alcohol, and polyhydric alcohols such as ethylene glycol,diethylene glycol, propylene glycol, glycerol, sorbitol, sorbitan andsimilar carbohydrates and derivatives of carbohydrates. When an ester isused as component B, it is converted to the magnesium salt of the freeacid during the reaction with component A and water. In other words, theacidic portion of the ester is the operative portion for the purpose ofthis invention and the identity of the alcoholic portion thereof isimmaterial. Thus, it will be appreciated that the equivalent weight ofthe ester for the purpose of this invention is its molecular weightdivided by the number of groups present therein which are convertible byhydrolysis to carboxylate or sulfonate groups or to pentavalentphosphorus acid groups under the reaction conditions of the invention.If any of the ester groups remain unconverted, the ester is consideredas inert to that extent for the purpose of calculating its equivalentweight.

The preferred compounds for use as component B are the above-describedsulfonic and carboxylic acids, especially those having an equivalentweight of about 300-500. The sulfonic acids are most often used, and aparticular preference is expressed for alkylaromatic sulfonic acids andmore particularly for alkylbenzenesulfonic acids.

It is also within the scope of the invention to use as component Bmixtures of two or more of the above-described compounds or types ofcompounds. Examples of suitable mixtures are mixtures of carboxylicacids, of sulfonic acids, and of sulfonic with carboxylic acids. Manysuch mixtures will be readily apparent to those skilled in the art.Particularly preferred are mixtures of alkylbenzenesulfonic acids withfatty acids (which may be hydrogenated) and with carboxylic acids formedby oxidation of hydrocarbons such a petrolatum.

One of the characteristics of component B is that it is oleophilic. Thismeans that it is soluble or at least stably dispersible (as definedhereinafter) in oil or similar non-polar organic liquids such as hexane,naphtha, Stoddard solvent, benzene, toluene and the like. Whilecomponent B need not be oil-soluble, the oil-soluble sulfonic andcarboxylic acids and phosphate esters are preferred for the purposes ofthis invention. These oil-soluble compounds constitute a known subgenusof the previously described compounds useful as component B.

COMPONENT C

Component C is water, which may be used in the liquid or vapor phase asdescribed hereinafter. For the purpose of the present invention, theequivalent weight of water is considered to be 9 (half its molecularweight).

COMPONENT D

Component D is at least one organic solubilizing agent for component B.It may be solid or liquid at room temperature, although liquids areoften preferred. It need not be a solvent for component B, in the sensethat component B is entirely soluble therein when in the liquid state,but should be at least a partial solvent in the sense that relativelysmall proportions of component B, at least, when blended with componentD in the liquid state will form a homogeneous mixture.

Materials useful as component D include substantially inert, normallyliquid organic diluents. The term "substantially inert" as used hereinis intended to mean that the diluent is inert to chemical or physicalchange under the conditions in which it is used so as not to materiallyinterfere in an adverse manner with the preparation, storage, blendingand/or functioning of the magnesium complex in the context of itsintended use. For example, small amounts of a diluent can undergominimal reaction or degradation without preventing the making and usingof the invention as described herein. In other words, such reaction ordegradation, while technically discernible, would not be sufficient todeter the practical worker of ordinary skill in the art from making andusing the invention for its intended purposes. "Substantially inert" asused herein is thus readily understood and appreciated by those ofordinary skill in the art.

Among the preferred normally liquid diluents are non-polar compounds ormixtures of compounds such as naphtha, hexane, kerosene, mineral oil,Stoddard solvent, benzene, toluene, xylene, and alkylbenzenes of thetype present as unsulfonated residue in alkylbenzenesulfonic acids. Alsosuitable are somewhat more polar liquids such as 1-butanol, 2-butanol,ethylene glycol, propylene glycol, ethylene glycol monomethyl ether,ethylene glycol monobutyl ether, ethylene glycol dimethyl ether,diethylene glycol and its ethers, wax-derived alcohol mixtures, methylethyl ketone, chlorobenzene, pyridine, indole, furan andtetrahydrofuran.

Also useful are materials which are chemically similar to theabove-described liquids but solid at ambient temperature. These includethe following, as well as mixtures of any two or more thereof:

Crystalline (including microcrystalline) and non-crystalline hydrocarbonwaxes, including natural hydrocarbon waxes such as petrolatum, paraffinand olefin waxes, and synthetic hydrocarbon waxes such as polyethyleneand other polyolefins.

Waxy alcohol mixtures such as C₂₀₋₄₀ aliphatic alcohols.

Resins such as styrene-butadiene copolymers, hydrogenatedstyrene-butadiene polymers, olefin-vinyl carboxylate (e.g., vinylacetate) copolymers, and hydrocarbon resins.

It is also within the scope of the invention to use mixtures of any ofthe materials described above. Such mixtures may be of materials all ofwhich are liquid at normal ambient temperatures (e.g., about 20°-30°C.), such as mineral oil-toluene, Stoddard solvent-toluene, mineraloil-alkylbenzene, Stoddard solvent-alkylbenzene; of materials all ofwhich are solid at normal ambient temperatures, such as paraffinwax-polyethylene wax, paraffin wax-polyethylene wax-C₂₀₋₄₀ alcohol wax;or of materials which are both liquid and solid at normal ambienttemperatures, such as mixtures of the above-mentioned normally liquiddiluents and a resin or hydrocarbon wax (e.g., paraffin wax-toluene,polypropylene-toluene, polypropylene-mineral oil).

COMPONENT PROPORTIONS

The relative proportions of components A, B, C and D are an importantfeature of this invention since the physical state in which themagnesium complex is obtained depends to a great extent on theproportions of the components used for their preparation.

As previously noted, the ratio of equivalents of magnesium to the acidportion of component B (free carboxylic or sulfonic acid, or acidicphosphoric acid ester) is at least about 5:1. This ratio is hereinaftersometimes referred to as the "magnesium ratio". (It will be appreciatedthat the magnesium ratio is such as to produce a basic magnesiumcomplex.) If component B is the free carboxylic acid, an ester thereof,a free sulfonic acid or an acidic phosphate ester, the ratio ofcomponent A to component B will be identical to the magnesium ratio. Ifcomponent B is a magnesium salt of one of the above, the ratio ofcomponent A to component B will be somewhat less than the magnesiumratio since part of the magnesium is provided by component B.

It has been found that magnesium complexes with relatively low magnesiumratios (e.g., about 5-25:1 and particularly about 5-10:1) areparticularly useful as lubricant additives. Complexes with a magnesiumratio above about 60:1 and preferably up to about 150:1 find utilityprincipally as additives for fuel oils. As protective coatings formetals, it is preferred to employ complexes in which component D isentirely or predominantly liquid and the magnesium ratio is betweenabout 25:1 and 60:1, or solid (e.g., "hot melt") complexes in whichcomponent D is entirely or predominantly solid at ambient temperatureand which typically have a magnesium ratio of about 5-50:1.

The molar ratio of water (component C) to component A (hereinaftersometimes designated the "water ratio") is also critical. It should beat least sufficient to hydrate a substantial proportion of component A,calculated as magnesium oxide. If component A is magnesium hydroxide, italready contains at least this amount of water and the amount ofadditional water will depend on the nature of the product desired andthe intended use thereof. On the other hand, if component A is anhydrousmagnesium oxide the water ratio should generally be at least about 0.7:1so as to produce the hydrated magnesium oxide referred to hereinabove.

Most often, a water ratio between about 0.7:1 and 3.0:1 is adequate toproduce a composition of this invention. If larger amounts of water thanthis are used, it is frequently possible to remove excess water, atleast some of which separates from the magnesium complex as a separatelayer and the remainder of which can be removed by azeotropicdistillation or the like. More water may be desirable for thepreparation of the complex in certain instances; for example, magnesiumoxide frequently contains traces of sodium compounds whose presence maybe undesirable in the complex, and if so, such compounds may be removedby using up to about 8 moles of water per mole of component A andremoving the excess, which has dissolved therein the sodium compounds.When the excess water has been removed, the molar ratio of remainingwater to component A is usually below about 3:1 as noted above.

As among various magnesium complexes with water ratios between about0.7:1 and 3.0:1, those having a water ratio below about 1:1 are oftenparticularly useful as lubricant additives or fuel oil additives, whilethose having a somewhat higher water ratio (e.g., between about 1:1 and3:1) may be particularly useful in the preparation ofcorrosion-resistant coating compositions.

The ratio of component D to component A is not critical and may bevaried so as to provide magnesium complexes suitable for the particularuse to which they are intended. For example, a complex suitable as alubricant additive may frequently be obtained by employing as componentD solely the unsulfonated alkylbenzene present as an impurity in thesulfonic acid used as component B. In that event, the weight ratio ofcomponent D to component A will usually be below about 1:1 andfrequently as low as 0.5-0.7:1. In general, when a lubricant additiveproduct is desired it is inadvisable to use volatile materials ascomponent D.

When the magnesium complex is to be used as a fuel oil additive, higheramounts of component D are frequently preferred and these may includerelatively volatile materials such as toluene or xylene, less volatilematerials such as mineral oil or mineral seal oil, and mixtures ofvolatile and less volatile materials. The proportions of volatile andnon-volatile solubilizing agents in such mixtures are subject to widevariation, but in any event it is usually found that the total weightratio of component D to component A should be about 1.2-1.8:1.

When a product useful in a protective metal coating is desired, stillhigher ratios (e.g., about 2-3:1) are often employed with one of thesolubilizing agents being a substantially volatile aliphatic hydrocarbonsuch as naphtha or Stoddard solvent, and the other being a somewhat lessvolatile material such as mineral oil. Another useful type of complexfor metal coating is the solid (e.g., "hot melt") type briefly referredto hereinabove, in which component D comprises mostly or entirelymaterials which are solid at ambient temperature, in which case theratio of D to A may be between about 0.5:1 and 6:1.

PREPARATION OF THE MAGNESIUM COMPLEX

The magnesium complexes of this invention are prepared by merelyblending the components described hereinabove and heating the resultingblend at a temperature above about 30° C. It is important that waterremain in the blend during substantially the entire period ofpreparation of the magnesium complex, and the maximum temperaturethereof should be adjusted accordingly. However, said water may bepresent in the liquid or vapor state, i.e., as liquid water or as steam,though it will be apparent to those skilled in the art that thepreparation of complexes involving a relatively large amount of waterwill be difficult if not impossible, at least at atmospheric pressure,if the water is present as steam. Therefore, it is generally found thattemperatures of about 30°-125° C. are most conveniently employed atatmospheric pressure, and the preparation should be carried out undersuperatmospheric pressure if the use of higher temperatures is likely.Most often, a maximum temperature of about 100° C. is convenient whencomponent D is entirely or predominantly liquid and the preferredtemperature range is then about 40°-90° C. Naturally, the temperaturemay be somewhat higher (e.g., about 95°-150° C.) when component D isentirely or predominantly a solid at ambient temperature.

The order of addition of the various components is not critical. It isoften convenient to first combine components A, B and D and subsequentlyto add component C (water) either all at once or incrementally. It isalso often found convenient to prepare an initial mixture containingonly a relatively small portion of component A (e.g., about 5-10% of thetotal amount thereof) and to add the remainder at a later stage,typically during or after the addition of water.

The magnesium complexes of this invention, when prepared as describedherein, are often conveniently obtained as thickened compositions, i.e.,viscous liquids or heterogeneous dispersions in the form of greases orgels, or (when component D is predominantly solid) as "hot melt"materials. For many purposes, such as the formation ofcorrosionresistant coatings, it is preferred that they be used in suchthickened or "hot melt" form. However, some other applications such asthose involving lubricants and fuels may require that the complex beobtained in the form of a relatively non-viscous, easily flowableliquid. Such liquids may be obtained by methods well known to those ofskill in the art, such as maximizing the amount of liquid diluentpresent as component D or by decreasing the relative amount of componentA or component C in the reaction mixture. Alternatively, a thickenedcomplex can be further diluted with a substantially inert organic liquiddiluent of the type described hereinabove to produce a homogeneoussolution. One of the unique and desirable characteristics of thecompositions of this invention is their capability of existing either asheterogeneous thickened compositions or homogeneous, relatively dilutesolutions or dispersion.

A method which is frequently advantageous for incorporating relativelylarge amounts of magnesium while making possible the formation of ahomogeneous solution or dispersion in mineral oil or the like is toprepare the complex in the presence of ammonium hydroxide, which may beprepared from ammonia and the water present as component C. The amountof ammonium hydroxide required is small, generally less than about 10%by weight based on the water present. Insoluble materials can then beremoved by diluting with a non-polar volatile organic liquid such ashexane or naphtha, centrifuging, and stripping the volatile liquid, orby equivalent means.

Another method for clarifying the magnesium complex for use in mineraloil, which may be employed in addition to or in place of preparation inthe presence of ammonium hydroxide, is to add water or an acidic orbasic reagent after preparation of the complex. The acidic or basicreagent may be organic or inorganic; suitable ones include sodiumhydroxide, potassium hydroxide, ammonium hydroxide, triethanolamine,tartaric acid and citric acid. The amount of water or acidic or basicreagent is generally less than about 10% by weight of the magnesiumcomplex system.

The molecular structures of the magnesium complexes of this inventionare not known and are not a critical aspect of the invention. Themagnesium complexes are, in general, most conveniently defined in termsof the method for their preparation.

The preparation of the magnesium complexes of this invention isillustrated by the following examples. All parts are by weight.

EXAMPLE 1

A blend is prepared of 135 parts of magnesium oxide and 600 parts of analkylbenzenesulfonic acid having an equivalent weight of about 385, andcontaining about 24% unsulfonated alkylbenzene. During blending, anexothermic reaction takes place which causes the temperature to rise to57° C. The mixture is stirred for one-half hour and then 50 parts ofwater is added. Upon heating at 95° C. for one hour, the desiredmagnesium oxide-sulfonate complex is obtained as a firm gel containing9.07% magnesium.

EXAMPLE 2

A blend of 600 parts of the alkylbenzenesulfonic acid of Example 1 and225 parts of magnesium oxide is prepared and heated for 2 hours at60°-65° C. There is then added, over one hour, a solution of 10 parts of30% ammonium hydroxide and 75 parts of water. The mixture is heated for3 hours at 60°-65° C., and then an additional 10 parts of 30% ammoniumhydroxide solution is added over 5 minutes. Upon heating for 2 morehours at 60°-65° C. and cooling, the desired magnesium oxide-sulfonatecomplex is obtained as a dark brown gel.

EXAMPLE 3

Following the procedure of Example 2, a blend is made of 600 parts ofthe alkylbenzenesulfonic acid of Example 1 and 225 parts of magnesiumoxide, and a solution of 30 parts of 30% ammonium hydroxide in 75 partsof water is added. After heating for 4 hours at 60°-65° C., the mixtureis cooled and 900 parts of hexane is added. The hexanediluted mixture iscentrifuged and the hexane is removed by vacuum stripping at 150° C. Theresidue is cooled to 130° C. and 18 parts of triethanolamine is added.The product is the desired magnesium oxide-sulfonate complex, a softbrown gel which contains 11.3% magnesium.

EXAMPLE 4

Magnesium hydroxide, 233 parts, is added to 600 parts of thealkylbenzenesulfonic acid of Example 1. There is then added 1250 partsof water and the mixture is heated gradually to about 80° C. over about2 hours, whereupon a gel forms. The mixture is allowed to stand and awater layer of 830 parts is decanted; 570 parts of toluene is then addedand an additional 300 parts of water is removed by azeotropicdistillation.

A 602-part portion of the resulting gel is diluted with 200 parts oftoluene. The solution is centrifuged and the toluene removed by blowingwith nitrogen at 160°-170° C. to yield the desired magnesiumoxide-sulfonate complex as a soft gel.

EXAMPLE 5

Magnesium oxide, 600 parts, is added to a solution in 478 parts ofStoddard solvent and 244 parts of mineral oil of 308 parts of analkylbenzenesulfonic acid having an equivalent weight of about 430 andcontaining about 22% unsulfonated alkylbenzene. Water, 381 parts, isadded and the mixture is heated under reflux for 15 minutes. It is thencooled to room temperature, yielding the desired magnesiumoxide-sulfonate complex in the form of a gel.

EXAMPLE 6

A mixture of 204 parts of the alkylbenzenesulfonic acid of Example 1, 88parts of mineral oil and 515 parts of Stoddard solvent is prepared, and320 parts of magnesium oxide is added, followed by 420 parts of water.The mixture is heated at 95°-100° C., with stirring, until gelationoccurs. The excess water (about 300 parts) is then removed by azeotropicdistillation to yeild the desired magnesium oxidesulfonate gel.

EXAMPLE 7

A mixture is prepared of 1106 parts of water, 54 parts of magnesiumoxide, 425 parts of the alkylbenzenesulfonic acid of Example 5, 495parts of mineral oil and 856 parts of Stoddard solvent. An additional781 parts of magnesium oxide is then added and the mixture is slowlyheated to 52°-55° C. There are then added 30 parts of tetrapropenylsuccinic acid and 37 parts of a black pigment. Upon screening andcooling, the desired composition containing the magnesiumoxide-sulfonate gel is obtained.

EXAMPLE 8

A mixture of 125 parts of toluene, 225 parts of the alkylbenzenesulfonicacid of Example 5, 680 parts of mineral oil, 550 parts of magnesiumoxide and 200 parts of water is heated slowly to reflux temperature(about 100° C.) and excess water (about 43 parts) is removed byazeotropic distillation. The residue is stripped under vacuum at 170° C.as 117 parts of volatiles are removed. The residue from the stripping iscooled to yield the desired magnesium oxidesulfonate complex in the formof a gel.

EXAMPLE 9

A mixture of 2050 parts of water, 30 parts of magnesium oxide, 294 partsof the alkylbenzenesulfonic acid of Example 5, and 520 parts of oil isheated to 35°-40° C., and an additional 715 parts of magnesium oxide isadded slowly. An exothermic reaction takes place and the magnesium oxideaddition is regulated so as to cause a temperature increase of about 10°C. per hour to a maximum temperature of about 65° C. Heating iscontinued until the temperature reaches 85° C., whereupon a gel isobtained containing a clear water layer on top. The excess water (about1552 parts) is decanted. To the residue are added 375 parts of mineraloil and 165 parts of toluene, and an additional portion of water (259parts) is removed by azeotropic distillation. Excess toluene is removedby stripping under nitrogen (180° C.) and the residue is screened toyield the desired magnesium oxidesulfonate gel.

EXAMPLE 10

A mixture of 900 parts of water, 333 parts of magnesium oxide, 266 partsof mineral oil and 132 parts of the alkylbenzenesulfonic acid of Example1 is heated to 80°-85° C., with stirring, over about 45 minutes. It ismaintained at this temperature for about 10-15 minutes after gelationtakes place, after which time stirring is discontinued and a water layerof about 793 parts is decanted. There are added 135 parts of mineral oiland 75 parts of toluene, and an additional 43 parts of water is removedby azeotropic distillation. The toluene is stripped at 180° C. bynitrogen blowing and the residue is screened to yield the desiredmagnesium oxide-sulfonate complex as a thick opaque liquid.

EXAMPLE 11

An acidic phosphate ester is prepared by adding 136 parts of methanoland 744 parts of a commercial mixture of predominantly straight chainC₁₂₋₁₄ alcohols to a suspension of 284 parts of phosphorus pentoxide in800 parts of hexane, with stirring. After the alcohols have been added,the reaction mixture is heated under reflux for 4 hours and hexane isremoved by distillation. The resulting acidic phosphate ester has anequivalent weight of about 200.

A mixture of 200 parts of the resulting acidic phosphate ester, 310parts of toluene, 880 parts of mineral oil and 440 parts of magnesiumoxide is prepared and heated to 60° C., with stirring, over 1/2 hour.Water, 200 parts, is then added and the mixture is heated at 94° C. for45 minutes, with continued stirring. Excess water is then removed byazeotropic distillation (a total of 90 parts) and the toluene is removedby vacuum stripping to yield the desired magnesium oxide-phosphatecomplex as a pourable gel.

EXAMPLE 12

A mixture of 754 parts of water, 23 parts of magnesium oxide, 210 partsof mineral oil and 247 parts of Stoddard solvent is heated to about 40°C. and 331 parts of a carboxylic acid having an equivalent weight ofabout 350 and obtained by oxidation of petrolatum, which acid has beenpreheated to about 50°-60° C., is added as the temperature of themixture is maintained at 40°-45° C. An additional 350 parts of magnesiumoxide is added, with stirring, and the temperature of the mixture isincreased to 75° C. An opaque dispersion is obtained which is screenedto afford the desired magnesium oxide-carboxylate complex.

EXAMPLE 13

A product similar to that of Example 12 is prepared, substituting about300 parts of sorbitan trioleate for the oxidized petrolatum.

EXAMPLE 14

A reaction vessel is charged with 63 parts of "Epal 20+", a solidmixture consisting predominantly of C₂₀₋₃₂ linear and branched aliphaticalcohols and available from Ethyl Corporation; 83 parts of "FactowaxR-143", a paraffin wax available from Standard Oil Company (Ohio) andmelting at about 62° C.; and 83 parts of "Bareco Polywax 655", apolyethylene synthetic wax manufactured by Petrolite Corp. and meltingat about 102° C. The mixture is melted and 21 parts of magnesium oxideis added. As the mixture is agitated at 96°-99° C., 235 parts of thealkylbenzenesulfonic acid of Example 5 is added. Following the sulfonicacid addition, an additional 185 parts of magnesium oxide is added at96°-99° C. Mixing is continued at that temperature for 2 hours and then69 parts of water is added over 2-1/2 hours at 99°-102° C. An additional76 parts of alkylbenzenesulfonic acid is added at 96-99° C. and mixingis continued for 1-1/2 hours after which the mixture is heated to143°-149° C. for 3 hours and blown with nitrogen to remove volatiles bydistillation. The residue is the desired solid magnesium oxide-sulfonatecomplex.

EXAMPLE 15

A mixture of 1280 parts of water, 18 parts of magnesium oxide, 180 partsof the alkylbenzenesulfonic acid of Example 5, and 215 parts of mineralseal oil is heated to 45° C. and an additional 534 parts of magnesiumoxide is added, with stirring. The mixture is heated to 80°-85° C. overtwo hours whereupon partial coagulation takes place and a water layerseparates. The water layer (about 1050 parts) is decanted and anadditional 290 parts of mineral seal oil is added. The mixture is purgedwith nitrogen at 140°-145° C. for 2-1/2 hours to remove excess water andis then passed through a 20-mesh screen to yield the desired magnesiumoxide-sulfonate complex.

EXAMPLE 16

A mixture of 16 parts of the alkylbenzenesulfonic acid of Example 5, 305parts of mineral oil, 180 parts of magnesium oxide and 96 parts of"Hydrex 440", a mixture of hydrogenated fatty acids obtainable fromUnion Camp Corporation, is heated to 95° C. and blown with steam for twohours. The temperature is increased to 145°-150° C., an additional 28parts of mineral oil is added and the mixture is blown with air as thetemperature is heated to 170° C. over 15 minutes. The mixture is thencooled to room temperature and an additional 44 parts of mineral oil isadded to yield the desired magnesium oxide-sulfonate complex having theconsistency of a grease.

LUBRICANTS AND FUELS

When in the form of flowable liquids as previously described, themagnesium complexes of this invention are stably dispersible in thenormally liquid media (e.g., oil, fuel, etc.) in which they are intendedto function. Thus, for example, compositions intended for use in oilsare stably dispersible in an oil in which they are to be used. The term"stably dispersible" as used in the specification and appended claims isintended to mean the magnesium complex or other material is capable ofbeing dispersed in a given medium to an extent which allows it tofunction in its intended manner. Thus, for example, when a magnesiumcomplex is used in an oil, it is sufficient that it be capable of beingsuspended in the oil in an amount sufficient to enable the oil topossess one or more of the desired properties imparted to it by thesuspended complex. Such suspension can be achieved in variousconventional ways. For example, in constantly circulating oil or oil insplash lubricating systems, physical agitation can keep the complexsuspended in oil. Likewise, conventional dispersants (such as theacrylated nitrogen dispersants disclosed in U.S. Pat. No. 3,219,666)often found in lubricating oils and fuels promote the stable dispersionor suspension of the magnesium complex. In any event, the complex willbe "stably dispersible" in the normally liquid media in which it will beused in at least the minimum concentrations set forth elsewhere herein.Thus, the terminology "stably dispersible" is used in a conventionalmanner and will be understood by those of ordinary skill in the art.

As previously indicated, the magnesium complexes of this invention maybe homogeneously incorporated into lubricants, in which they functionprimarily as ashproducing detergents. The products of Examples 1-4 areparticularly useful for this purpose. They can be employed in a varietyof lubricants based on diverse oils of lubricating viscosity, includingnatural and synthetic lubricating oils and mixtures thereof. Theselubricants include crankcase lubricating oils for spark-ignited andcompression-ignited internal combustion engines, including automobileand truck engines, two-cycle engines, aviation piston engines, marineand railroad diesel engines, and the like. They can also be used in gasengines, stationary power engines and turbines and the like. Automatictransmission fluids, transaxle lubricants, gear lubricants,metal-working lubricants, hydraulic fluids and other lubricating oil andgrease compositions can also benefit from the incorporation therein ofthe magnesium complexes of the present invention.

Natural oils include animal oils and vegetable oils (e.g., castor oil,lard oil) as well as liquid petroleum oils and solvent-treated oracid-treated mineral lubricating oils of the paraffinic, naphthenic ormixed paraffinic-naphthenic types. Oils of lubricating viscosity derivedfrom coal or shale are also useful base oils. Synthetic lubricating oilsinclude hydrocarbon oils and halosubstituted hydrocarbon oils such aspolymerized and interpolymerized olefins [e.g., polybutylenes,polypropylenes, propylene-isobutylene copolymers, chlorinatedpolybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes), etc.and mixtures thereof]; alkylbenzenes [e.g., dodecylbenzenes,tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes, etc.];polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.),alkylated diphenyl ethers and alkylated diphenyl sulfides and thederivatives, analogs and homologs thereof and the like.

Alkylene oxide polymers and interpolymers and derivatives thereof wherethe terminal hydroxyl groups have been modified by esterification,etherification, etc. constitute another class of known syntheticlubricating oils. These are exemplified by the oils prepared throughpolymerization of ethylene oxide or propylene oxide, the alkyl and arylethers of these polyoxyalkylene polymers (e.g., methylpolyisopropyleneglycol ether having an average molecular weight of 1000, diphenyl etherof polyethylene glycol having a molecular weight of 500-1000, diethylether of polypropylene glycol having a molecular weight of 1000-1500,etc.) or mono- and polycarboxylic esters thereof, for example, theacetic acid esters, mixed C₃ -C₈ fatty acid esters, or the C₁₃ Oxo aciddiester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acids and alkenyl succinic acids, maleic acid, azelaic acid,suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic aciddimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.)with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycolmonoether, propylene glycol, etc.). Specific examples of these estersinclude dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate,dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctylphthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyldiester of linoleic acid dimer, the complex ester formed by reacting onemole of sebacic acid with two moles of tetraethylene glycol and twomoles of 2-ethylhexanoic acid, and the like.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylolpropane, pentaerythritol, dipentaerythritol,tripentaerythritol, etc.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxy-siloxane oils and silicate oils comprise another usefulclass of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropylsilicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butylphenyl) silicate,hexyl-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)siloxanes,poly(methylphenyl)siloxanes, etc.). Other synthetic lubricating oilsinclude liquid esters of phosphorus-containing acids (e.g., tricresylphosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid,etc.), polymeric tetrahydrofurans and the like.

Unrefined, refined and rerefined oils (and mixtures of each with eachother) of the type dislosed hereinabove can be used in the lubricantcompositions of the present invention. Unrefined oils are those obtaineddirectly from a natural or synthetic source without further purificationtreatment. For example, a shale oil obtained directly from retortingoperations, a petroleum oil obtained directly from distillation or esteroil obtained directly from an esterification process and used withoutfurther treatment would be an unrefined oil. Refined oils are similar tothe unrefined oils except they have been further treated in one or morepurification steps to improve one or more properties. Many suchpurification techniques are known to those of skill in the art such assolvent extraction, acid or base extraction, filtration, percolation,etc. Rerefined oils are obtained by processes similar to those used toobtain refined oils applied to refined oils which have been already usedin service. Such rerefined oils are also known as reclaimed orreprocessed oils and often are additionally processed by techniquesdirected to removal of spent additives and oil breakdown products.

Generally, the lubricants of the present invention contain an amount ofthe composition of this invention sufficient to impart detergencythereto. Normally this amount will be about 0.05-20.0%, preferably about0.5-10.0%, of the total weight of the lubricant. In lubricating oilsoperated under extremely adverse conditions, such as lubricating oilsfor marine diesel engines, the magnesium complexes of this invention maybe present in amounts up to about 30%.

The magnesium complexes of the present invention, as illustrated by theproducts of Examples 8-10 and 15, are also useful as corrosioninhibitors, vanadium scavengers and smoke suppressants in fuels. Forthat purpose, they are homogeneously incorporated in minor proportionsin normally liquid fuels, usually hydrocarbonaceous fuels such as fueloils, bunker fuels and the like. Normally liquid fuel compositionscomprising non-hydrocarbonaceous materials such as alcohols, ethers,organo-nitro compounds and the like (e.g., methanol, ethanol, diethylether, methyl ethyl ether, nitromethane) are also within the scope ofthe invention as are liquid fuels derived from vegetable or mineralsources such as corn, alfalfa, shale and coal. Normally liquid fuelswhich are mixtures of one or more hydrocarbonaceous fuels and one ormore non-hydrocarbonaceous materials are also contemplated.

Generally, these fuel compositions contain an amount of the magnesiumcomplex sufficient to impart corrosion-resistance thereto, suppresssmoke or serve as a vanadium scavenger; usually this amount is about1-10,000, preferably 4-1000, parts thereof by weight per million partsof fuel.

The invention also contemplates the use of other additives incombination with the magnesium complexes. Other additives useful inlubricants include, for example, auxiliary detergents and dispersants ofthe ash-producing or ashless type, corrosion- and oxidation-inhibitingagents, pour point depressing agents, extreme pressure agents, colorstabilizers and anti-foam agents.

The auxiliary ash-producing detergents are exemplified by oil-solubleneutral and basic salts of alkali or alkaline earth metals with sulfonicacids, carboxylic acids, or organic phosphorus acids characterized by atleast one direct carbon-to-phosphorus linkage such as those prepared bythe treatment of an olefin polymer (e.g., polyisobutene having amolecular weight of 1000) with a phosphorizing agent such as phosphorustrichloride, phosphorus heptasulfide, phosphorus pentasulfide,phosphorus trichloride and sulfur, white phosphorus and a sulfur halide,or phosphorothioic chloride. The most commonly used salts of such acidsare those of sodium, potassium, lithium, calcium, magnesium, strontiumand barium.

The term "basic salt" is used to designate metal salts wherein the metalis present in stoichiometrically larger amounts than the organic acidradical. The commonly employed methods for preparing the basic saltsinvolve heating a mineral oil solution of an acid with a stoichiometricexcess of a metal neutralizing agent such as the metal oxide, hydroxide,carbonate, bicarbonate, or sulfide at a temperature above 50° C. andfiltering the resulting mass. The use of a "promoter" in theneutralization step to aid the incorporation of a large excess of metallikewise is known. Examples of compounds useful as the promoter includephenolic substances such as phenol, naphthol, alkylphenol, thiophenol,sulfurized alkylphenol, and condensation products of formaldehyde with aphenolic substance; alcohols such as methanol, 2-propanol, octylalcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, andcyclohexyl alcohol; and amines such as aniline, phenylenediamine,phenothiazine, phenyl-β-naphthylamine, and dodecylamine. A particularlyeffective method for preparing the basic salts comprises mixing an acidwith an excess of a basic alkaline earth metal neutralizing agent and atleast one alcohol promoter, and carbonating the mixture at an elevatedtemperature such as 60° -200° C.

Ashless detergents and dispersants are so called despite the fact that,depending on its constitution, the dispersant may upon combustion yielda non-volatile material such as boric oxide or phosphorus pentoxide;however, it does not ordinarily contain metal and therefore does notyield a metal-containing ash on combustion. Many types are known in theart, and any of them are suitable for use in the lubricants of thisinvention. The following are illustrative:

(1) Reaction products of carboxylic acids (or derivatives thereof)containing at least about 34 and preferably at least about 54 carbonatoms with nitrogen-containing compounds such as amine, organic hydroxycompounds such as phenols and alcohols, and/or basic inorganicmaterials. Examples of these "carboxylic dispersants" are described inBritish Pat. No. 1,306,529 and in many U.S. Pat. Nos. including thefollowing:

    ______________________________________                                        3,163,603  3,351,552     3,541,012                                            3,184,474  3,381,022     3,542,678                                            3,215,707  3,399,141     3,542,680                                            3,219,666  3,415,750     3,567,637                                            3,271,310  3,433,744     3,574,101                                            3,272,746  3,444,170     3,576,743                                            3,281,357  3,448,048     3,630,904                                            3,306,908  3,448,049     3,632,510                                            3,311,558  3,451,933     3,632,511                                            3,316,177  3,454,607     3,697,428                                            3,340,281  3,467,668     3,725,441                                            3,341,542  3,501,405     Re 26,433                                            3,346,493  3,522,179                                                          ______________________________________                                    

(2) Reaction products of relatively high molecular weight aliphatic oralicyclic halides with amines, preferably polyalkylene polyamines. Thesemay be characterized as "amine dispersants" and examples thereof aredescribed for example, in the following U.S. Pat. Nos.:

    ______________________________________                                        3,275,554       3,454,555                                                     3,438,757       3,565,804                                                     ______________________________________                                    

(3) Reaction products of alkyl phenols in which the alkyl group containsat least about 30 carbon atoms with aldehydes (especially formaldehyde)and amines (especially polyalkylene polyamines), which may becharacterized as "Mannich dispersants". The materials described in thefollowing U.S. Pat. Nos. are illustrative.

    ______________________________________                                        3,413,347       3,725,480                                                     3,697,574       3,726,882                                                     3,725,277                                                                     ______________________________________                                    

(4) Products obtained by post-treating the carboxylic, amine or Mannichdispersants with such reagents as urea, thiourea, carbon disulfide,aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinicanhydrides, nitriles, epoxides, boron compounds, phosphorus compounds orthe like. Exemplary materials of this kind are described in thefollowing U.S. Pat. Nos.:

    ______________________________________                                        3,036,003                                                                              3,282,955  3,493,520   3,639,242                                     3,087,936                                                                              3,312,619  3,502,677   3,649,229                                     3,200,107                                                                              3,366,569  3,513,093   3,649,659                                     3,216,936                                                                              3,367,943  3,533,945   3,658,836                                     3,254,025                                                                              3,373,111  3,539,633   3,697,574                                     3,256,185                                                                              3,403,102  3,573,010   3,702,757                                     3,278,550                                                                              3,442,808  3,579,450   3,703,536                                     3,280,234                                                                              3,455,831  3,591,598   3,704,308                                     3,281,428                                                                              3,455,832  3,600,372   3,708,522                                     ______________________________________                                    

(5) Interpolymers of oil-solubilizing monomers such as decylmethacrylate, vinyl decyl ether and high molecular weight olefins withmonomers containing polar substituents, e.g., aminoalkyl acrylates oracrylamides and poly-(oxyethylene)-substituted acrylates. These may becharacterized as "polymeric dispersants" and examples thereof aredisclosed in the following U.S. Pat. Nos.:

    ______________________________________                                        3,329,658       3,666,730                                                     3,449,250       3,687,849                                                     3,519,565       3,702,300                                                     ______________________________________                                    

The above-noted patents are incorporated by reference herein for theirdisclosures of ashless dispersants.

Extreme pressure agents and corrosion- and oxidation-inhibiting agentsare exemplified by chlorinated aliphatic hydrocarbons such aschlorinated wax; organic sulfides and polysulfides such as benzyldisulfide, bis(chloro-benzyl)disulfide, dibutyl tetrasulfide, sulfurizedmethyl ester of oleic acid, sulfurized alkylphenol, sulfurizeddipentene, and sulfurized terpene; phosphosulfurized hydrocarbons suchas the reaction product of a phosphorus sulfide with turpentine ormethyl oleate; phosphorus esters including principally dihydrocarbon andtrihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite,dicyclohexyl phosphite, pentyl phenyl phosphite, dipentyl phenylphosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthylphosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecularweight 500)-substituted phenyl phosphite, diisobutyl-substituted phenylphosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate,and barium heptylphenyl dithiocarbamate; Group II metalphosphorodithioates such as zinc dicyclohexylphosphorodithioate, zincdioctylphosphorodithioate, barium di(heptylphenyl)-phosphorodithioate,cadmium dinonylphosphorodithioate, and the zinc salt of aphosphorodithioic acid produced by the reaction of phosphoruspentasulfide with an equimolar mixture of isopropyl alcohol and n-hexylalcohol.

Other additives useful in fuels include deposit preventers or modifierssuch as triaryl phosphates, dyes, cetane improvers, antioxidants such as2,6-di-tertiary-butyl-4-methylphenol, rust inhibitors such as alkylatedsuccinic acids and anhydrides, bacteriostatic agents, gum inhibitors,metal deactivators, demulsifiers and the like.

The magnesium complexes of this invention can be added directly to thelubricant or fuel. Preferably, however, they are diluted with asubstantially inert, normally liquid organic diluent such as thosementioned hereinabove, particularly mineral oil, naphtha, benzene,toluene or xylene, to form an additive concentrate. These concentratesgenerally contain about 20-90% by weight of the magnesium complex andmay contain in addition, one or more of the other additives describedhereinabove.

The lubricants of this invention are illustrated by the followingexample. All parts are by weight.

EXAMPLE 17

    ______________________________________                                        Ingredient                Parts                                               ______________________________________                                        Mineral oil (SAE 10W-40 base)                                                                           86.83                                               Product of Example 4      0.49                                                Mixed ester-amide of polybutenyl                                              succinic acid             3.02                                                Zinc dialkylphosphorodithioate                                                                          0.82                                                Sulfurized alkyl cyclohexenecarboxylate                                                                 0.39                                                Tetrapropenylsuccinic acid                                                                              0.07                                                Ethoxylated alkyl phenol  0.29                                                Hindered phenol antioxidant                                                                             0.34                                                Polyacrylate viscosity index improver                                                                   7.75                                                Silicone anti-foam agent  0.01                                                ______________________________________                                    

CORROSION-RESISTANT COATINGS AND OTHER USES

The thickened magnesium complexes of this invention are useful ascorrosion-resistant coatings for metal (e.g., ferrous metal, galvanized,aluminum or magnesium) surfaces, especially in the nature of undercoatsfor automotive bodies, coatings for structural members such asautomotive frames, and the like. They may be employed as such alone, incombination with other basic metal sulfonates and the like known to beuseful in corrosion-resistant coatings, and/or in combination with knownadjuvants for such corrosion-resistant coatings such as acidic phosphateesters, resins, and waxes. Many of the suitable resins and waxes are thesame as those described hereinabove with reference to component D; theymay be incorporated in varying amounts in the thickened complex butgenerally comprise a minor amount of the coating composition. U.S. Pat.Nos. 3,453,124 and 3,671,072 are incorporated by reference herein fortheir disclosures of basic compositions and adjuvants useful incombination with the thickened magnesium complexes.

The products of Examples 5-7 are exemplary of the magnesium complexessuitable for use as corrosion-resistant coatings of the undercoat type.Also useful for this purpose is the product prepared by the followingexample.

EXAMPLE 18

A product is obtained substantially in accordance with the procedure ofExample 7 by the reaction of 11.61 parts of the alkylbenzenesulfonicacid of Example 5, 9.2 parts of mineral oil, 23.71 parts of Stoddardsolvent, 22.61 parts of magnesium oxide and 30.92 parts of water. To theresulting gel are added 0.97 part of a black pigment composition and 1.0part of a vinyl acetate-ethylene copolymer comprising about 28% vinylacetate units.

For coating automotive frames and the like, a solid "hot melt"composition of the type described in Example 14 is particularlysuitable. Frequently, a dye or pigment is added to the "hot melt"composition; for example, 17 parts of a black pigment may be added tothe product of Example 14 immediately after the distillation step anddistillation may then be continued to remove volatiles present in thedye or pigment composition.

For corrosion-inhibiting purposes, the thickened or solid composition ofthis invention may be applied to the metal surface by any ordinarymethod such as brushing, spraying, dip-coating, flow-coating,roller-coating and the like, with heating if necessary (as to liquefy asolid composition). The viscosity of a thickened composition may beadjusted for the particular method of application selected by adding, ifnecessary, a substantially inert, normally liquid organic diluent suchas those disclosed hereinabove. The coated metal surface may then bedried either by exposure to air or by baking, although drying frequentlytakes place without a separate drying step. If the coating compositionis of a suitable viscosity to allow direct application to the metalsurface, typically the consistency of a No. 1 or No. 2 grease, nosolvent is used and no drying procedure need be followed. A more viscousgrease can be diluted to produce a less viscous grease which is suitablefor application as previously noted. The film thickness is not criticalalthough a coating of about 50-2000 mg. per square foot of surface inthe case of an undercoat, and up to about 10,000 mg. per square foot inthe case of a coating for frames or other structural members, is usuallysufficient to provide adequate protection. Heavier coatings can be usedif desired, but they normally contribute little in the way of additionalprotection.

The magnesium complexes of this invention are also useful as lubricantgreases and as stabilizers for resinous compositions, typicallypolyvinyl chloride, to protect them against oxidative degradation.

What is claimed is:
 1. A method for preparing a non-carbonatedmagnesium-containing complex which comprises heating, at a temperatureabove about 30° C., a mixture comprising:(A) At least one of magnesiumhydroxide, magnesium oxide, hydrated magnesium oxide, or a magnesiumalkoxide; (B) At least one oleophilic organic reagent comprising acarboxylic acid, a sulfonic acid, a pentavalent phosphorus acid, or anester or alkali metal or alkaline earth metal salt of any of these; (C)Water; and (D) At least one organic solubilizing agent for component B;the ratio of equivalents of magnesium to component B, calculated as thefree carboxylic or sulfonic acid or as the phosphoric acid ester, beingat least about 5:1, and the amount of water present being at leastsufficient to hydrate a substantial proportion of component A calculatedas magnesium oxide.
 2. A method according to claim 1 wherein component Dis at least one substantially inert, normally liquid organic diluent. 3.A method according to claim 2 wherein component B is at least onesulfonic acid or salt thereof.
 4. A method according to claim 3 whereinthe molar ratio of component C to component A is at least about 0.7:1.5. A method according to claim 4 wherein component B is at least onealkylaromatic sulfonic acid.
 6. A method according to claim 5 whereincomponent B is at least one alkylbenzenesulfonic acid.
 7. A methodaccording to claim 6 wherein component A is magnesium oxide.
 8. A methodaccording to claim 2 wherein component B is a mixture of at least onealkylbenzenesulfonic acid and at least one hydrogenated fatty acid orcarboxylic acid formed by oxidation of petrolatum.
 9. A method accordingto claim 8 wherein the mole ratio of component C to component A is atleast about 0.7:1.
 10. A method according to claim 9 wherein component Ais magnesium oxide.
 11. A method according to claim 1 wherein componentD is at least one substantially inert organic material which is solid atambient temperature.
 12. A method according to claim 11 whereincomponent B is at least one sulfonic acid or salt thereof.
 13. A methodaccording to claim 12 wherein the molar ratio of component C tocomponent A is at least about 0.7:1.
 14. A method according to claim 13wherein component B is at least one alkylaromatic sulfonic acid.
 15. Amethod according to claim 14 wherein component B is at least onealkylbenzenesulfonic acid.
 16. A method according to claim 15 whereincomponent A is magnesium oxide.
 17. A method according to claim 1wherein component D is a mixture of at least one substantially inertmaterial which is solid at ambient temperature with at least onesubstantially inert, normally liquid organic diluent.
 18. A methodaccording to claim 17 wherein component B is at least one sulfonic acidor a magnesium salt thereof.
 19. A method according to claim 18 whereinthe molar ratio of component C to component A is at least about 0.7:1.20. A method according to claim 19 wherein component B is at least onealkylaromatic sulfonic acid.
 21. A method according to claim 20 whereincomponent B is at least one alkylbenzenesulfonic acid.
 22. A methodaccording to claim 21 wherein component A is magnesium oxide.
 23. Amethod according to claim 17 wherein component B is a mixture of atleast one alkylbenzenesulfonic acid and at least one carboxylic acidformed by oxidation of petrolatum.
 24. A method according to claim 23wherein the mole ratio of component C to component A is at least about0.7:1.
 25. A method according to claim 24 wherein component A ismagnesium oxide.
 26. A complex prepared by the method of claim
 1. 27. Acomplex prepared by the method of claim
 3. 28. A complex prepared by themethod of claim
 5. 29. A complex prepared by the method of claim
 6. 30.A complex prepared by the method of claim
 8. 31. A complex which issolid at ambient temperature, prepared by the method of claim
 11. 32. Acomplex which is solid at ambient temperature, prepared by the method ofclaim
 12. 33. A complex which is solid at ambient temperature, preparedby the method of claim
 14. 34. A complex which is solid at ambienttemperature, prepared by the method of claim
 15. 35. A thickened complexaccording to claim
 26. 36. A thickened complex according to claim 27.37. A thickened complex according to claim
 28. 38. A thickened complexaccording to claim
 29. 39. A thickened complex according to claim 30.40. A thickened complex prepared by the method of claim
 17. 41. Athickened complex prepared by the method of claim
 18. 42. A thickenedcomplex prepared by the method of claim
 20. 43. A thickened complexprepared by the method of claim
 21. 44. A thickened complex prepared bythe method of claim
 23. 45. A complex of magnesium oxide or hydroxideand a magnesium sulfonate prepared by heating, at a temperature withinthe range of about 40°-90° C., a mixture comprising:(A) Magnesium oxide;(B) An alkylbenzenesulfonic acid having an equivalent weight within therange of about 300-500; (C) Water; and (D) At least one of mineral oil,Stoddard solvent, toluene and the alkylbenzene whose sulfonation productis component B; the ratio of equivalents of component A to component Bbeing at least about 5:1 and the molar ratio of component C to componentA being between about 0.7:1 and 3.0:1.
 46. A thickened complex accordingto claim
 45. 47. A complex of magnesium oxide or hydroxide and amagnesium sulfonate which is solid at ambient temperature and which isprepared by heating, at a temperature within the range of about 95°-150°C., a mixture comprising:(A) Magnesium oxide; (B) Analkylbenzenesulfonic acid having an equivalent weight within the rangeof about 300-500; (C) Water; and (D) A mixture comprising hydrocarbonwaxes, C₂₀₋₄₀ waxy aliphatic alcohols and the alkylbenzene whosesulfonation product is component B; the ratio of equivalents ofcomponent A to component B being at least about 5:1 and the molar ratioof component C to component A being between about 0.7:1 and 3.0:1. 48.An additive concentrate comprising a substantially inert, normallyliquid organic diluent and about 20-90% by weight of the complex ofclaim
 26. 49. An additive concentrate comprising a substantially inert,normally liquid organic diluent and about 20-90% by weight of thecomplex of claim
 45. 50. A composition comprising a major amount of alubricating oil and a minor amount sufficient to impart detergencythereto of the complex of claim
 26. 51. A composition comprising a majoramount of a lubricating oil and a minor amount, sufficient to impartdetergency thereto and comprising about 0.5-10.0% by weight, of thecomplex of claim
 45. 52. A composition comprising a major amount of anormally liquid fuel and a minor amount, sufficient to impart corrosionresistance thereto, suppress smoke or serve as a vanadium scavenger, ofthe complex of claim
 26. 53. A composition comprising a major amount ofa normally liquid fuel and a minor amount, sufficient to impartcorrosion resistance thereto, suppress smoke or serve as a vanadiumscavenger and comprising about 4-1000 parts by weight per million partsof fuel, of the complex of claim 45.